Catalyst composition with halo-malonate internal electron donor and polymer from same

ABSTRACT

Disclosed herein are procatalyst compositions, catalyst compositions and polymers, i.e., propylene-based polymers, produced therefrom. The present procatalyst compositions contain a halo-malonate and a 2-fluoro-malonate in particular. The present catalyst compositions improve catalyst selectivity, improve catalyst activity, and also improve hydrogen response during polymerization. Propylene-based polymer produced from the present catalyst composition has a melt flow rate greater than 50 g/10 min.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. application Ser.No. 12/974,402, filed on Dec. 21, 2010, now U.S. Pat. No. 8,383,540, theentire content of which is incorporated by reference herein.

BACKGROUND

The present disclosure provides a process for enhancing procatalyst andcatalyst properties. The present disclosure provides formant polymersproduced by these procatalysts/catalysts.

Worldwide demand for olefin-based polymers continues to grow asapplications for these polymers become more diverse and moresophisticated. Known are Ziegler-Natta catalyst compositions for theproduction of olefin-based polymers and propylene-based polymers inparticular. Ziegler-Natta catalyst compositions typically include aprocatalyst containing a transition metal halide (i.e., titanium,chromium, vanadium), a cocatalyst such as an organoaluminum compound,and optionally an external electron donor. Many conventionalZiegler-Natta catalyst compositions include a magnesiumchloride-supported titanium chloride procatalyst with a phthalate-basedinternal electron donor.

The health concerns from phthalate exposure are driving the art to findphthalate substitutes. Known are catalyst compositions containing amalonate or halo-malonate as an internal electron donor for producingpropylene-based polymers. The art recognizes the need for additionalhalo-malonates suitable as phthalate substitutes in olefinpolymerization catalysts.

SUMMARY

The present disclosure provides a Ziegler-Natta procatalyst compositioncontaining a halo-malonate as an internal electron donor. The Applicanthas discovered that fluorination, alone or in combination with alkylsubstitution of the malonate central carbon atom, unexpectedly improvescatalyst selectivity and/or catalyst activity. Applicant has furtherdiscovered that a procatalyst composition with a mixed internal electrondonor composed of a halo-malonate in combination with an electron donorcomponent also unexpectedly improves catalyst selectivity and/orcatalyst activity.

In addition to improved catalyst properties, the present procatalystcompositions further exhibit desirable process characteristics (highhydrogen response, high catalyst activity) and produces olefin-basedpolymer, such as propylene-based polymers with low xylene solubles, highT_(MF), good morphology and expanded in-reactor melt flow range.

The disclosure provides a procatalyst composition. In an embodiment, aprocatalyst composition is provided and includes a magnesium moiety, atitanium moiety, and an internal electron donor. The internal electrondonor includes a fluoro-malonate with the structure (II) below.

R₁ and R₂ are the same or different. Each of R₁ and R₂ is selected froma C₁-C₂₀ hydrocarbyl group and an unsubstituted C₁-C₂₀ hydrocarbylgroup. In an embodiment, the fluoro-malonate is a compoundedfluoro-malonate.

The disclosure provides another procatalyst composition. In anembodiment, a procatalyst composition is provided and includes amagnesium moiety, a titanium moiety, and a mixed internal electrondonor. The mixed internal electron donor includes a halo-malonate and anelectron donor component. The halo-malonate has the structure (II)below.

R₁ and R₂ are the same or different. Each of R₁ and R₂ is selected froma C₁-C₂₀ hydrocarbyl group and an unsubstituted C₁-C₂₀ hydrocarbylgroup. X is selected from fluorine, chlorine, bromine, and iodine. In anembodiment, the mixed internal electron donor is a compounded mixedinternal electron donor.

The disclosure provides a catalyst composition. In an embodiment, acatalyst composition is provided and includes a procatalyst composition,a cocatalyst, and optionally an external electron donor. The procatalystcomposition contains a halo-malonate as disclosed herein.

The disclosure provides a polymeric composition. In an embodiment, apolymeric composition is provided and includes a propylene-based polymerwhich contains a halo-malonate with the structure (II) below.

R₁ is selected from a C₃-C₂₀ secondary alkyl group, a C₄-C₂₀ tertiaryalkyl group, a C₆-C₂₀ aryl group, and a C₇-C₂₀ alkylaryl group. R₂ isselected from a C₁-C₂₀ primary alkyl group and a substituted orunsubstituted C₂-C₂₀ 1-alkenyl group. X is selected from fluorine,chlorine, bromine, and iodine. The propylene-based polymer has a meltflow rate greater than 50 g/10 min.

In an embodiment, the propylene-based polymer has a xylene solublescontent from 1 wt % to 4 wt %.

In an embodiment, the propylene-based polymer contains fluorine with Xbeing fluorine.

An advantage of the present disclosure is the provision of an improvedprocatalyst composition.

An advantage of the present disclosure is the provision of a procatalystcomposition with improved selectivity for the polymerization ofolefin-based polymers.

An advantage of the present disclosure is a phthalate-free procatalystcomposition.

An advantage of the present disclosure is the provision of aphthalate-free catalyst composition and a phthalate-free olefin-basedpolymer produced therefrom.

DETAILED DESCRIPTION

The present disclosure provides a procatalyst composition containing ahalo-malonate as an internal electron donor. The present catalystcomposition improves one or more of the following catalyst properties:activity, selectivity, and/or hydrogen response to producepropylene-based polymer with low xylene solubles, high T_(MF),acceptable polydispersity and/or high melt flow.

In an embodiment, a procatalyst composition is provided. The procatalystcomposition is a combination of a magnesium moiety, a titanium moiety,and a 2-halo-malonate such as a 2-fluoro-malonate.

Procatalyst Precursor

The procatalyst composition is formed by one, two, three, or morecontacts between a procatalyst precursor and a halogenating agent in thepresence of a halo-malonate (internal electron donor). The procatalystprecursor contains magnesium and may be a magnesium moiety compound(MagMo), a mixed magnesium titanium compound (MagTi), or abenzoate-containing magnesium chloride compound (BenMag). In anembodiment, the procatalyst precursor is a magnesium moiety (“MagMo”)precursor. The “MagMo precursor” contains magnesium as the sole metalcomponent. The MagMo precursor includes a magnesium moiety. Nonlimitingexamples of suitable magnesium moieties include anhydrous magnesiumchloride and/or its alcohol adduct, magnesium alkoxide or aryloxide,mixed magnesium alkoxy halide, and/or carbonated magnesium dialkoxide oraryloxide. In one embodiment, the MagMo precursor is a magnesiumdi(C₁₋₄)alkoxide. In a further embodiment, the MagMo precursor isdiethoxymagnesium.

In an embodiment, the procatalyst precursor is a mixedmagnesium/titanium compound (“MagTi”). The “MagTi precursor” has theformula Mg_(d)Ti(OR^(e))_(f)X_(g) wherein R^(e) is an aliphatic oraromatic hydrocarbon radical having 1 to 14 carbon atoms or COR′ whereinR′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbonatoms; each OR^(e) group is the same or different; X is independentlychlorine, bromine or iodine, preferably chlorine; d is 0.5 to 56, or 2to 4; f is 2 to 116 or 5 to 15; and g is 0.5 to 116, or 1 to 3. TheMagTi precursor is prepared by controlled precipitation through removalof an alcohol from the precursor reaction medium used in theirpreparation. In an embodiment, a reaction medium comprises a mixture ofan aromatic liquid, such as a chlorinated aromatic compound, orchlorobenzene, with an alkanol, especially ethanol. Suitablehalogenating agents include titanium tetrabromide, titaniumtetrachloride or titanium trichloride, especially titaniumtetrachloride. Removal of the alkanol from the solution used in thehalogenation, results in precipitation of the solid precursor, havingdesirable morphology and surface area. In a further embodiment, theresulting procatalyst precursor is a plurality of particles that areuniform in particle size.

In an embodiment, the procatalyst precursor is a benzoate-containingmagnesium chloride material. As used herein, a “benzoate-containingmagnesium chloride” (“BenMag”) can be a procatalyst (i.e., a halogenatedprocatalyst precursor) containing a benzoate internal electron donor.The BenMag material may also include a titanium moiety, such as atitanium halide. The benzoate internal donor is labile and can bereplaced by other electron donors during procatalyst and/or catalystsynthesis. Nonlimiting examples of suitable benzoate groups includeethyl benzoate, methyl benzoate, ethyl p-methoxybenzoate, methylp-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl p-chlorobenzoate. In oneembodiment, the benzoate group is ethyl benzoate. Nonlimiting examplesof suitable BenMag procatalyst precursors include catalysts of the tradenames SHAC™ 103 and SHAC™ 310 available from The Dow Chemical Company,Midland, Mich. In an embodiment, the BenMag procatalyst precursor may bea product of halogenation of any procatalyst precursor (i.e., a MagMoprecursor or a MagTi precursor) in the presence of a benzoate compound.

In a further embodiment, the procatalyst precursor is a solid materialthat contains chlorine. The chlorine-containing solid procatalystprecursor can be a MagMo compound, a MagTi compound, or a BenMagcompound.

Procatalyst Composition

The procatalyst precursor is contacted one, two, three, or more timeswith a halogenating agent in the presence of halo-malonate to form theprocatalyst composition. The halo-malonate is an internal electrondonor. As used herein, an “internal electron donor” (or “IED”) is acompound added or otherwise formed during formation of the procatalystcomposition that donates at least one pair of electrons to one or moremetals present in the resultant procatalyst composition. Not wishing tobe bound by any particular theory, it is believed that duringhalogenation (and titanation) the internal electron donor (1) regulatesthe formation of active sites and thereby enhances catalyststereoselectivity, (2) regulates the position of titanium on themagnesium-based support, (3) facilitates conversion of the magnesium andtitanium moieties into respective halides and (4) regulates thecrystallite size of the magnesium halide support during conversion.Thus, provision of the internal electron donor yields a procatalystcomposition with enhanced stereoselectivity. The internal electron donoris one, two, or more halo-malonate(s).

The term “contacting,” or “contact,” or “contact step” in the context ofprocatalyst synthesis, is the chemical reaction that occurs in areaction mixture (optionally heated) containing a procatalystprecursor/intermediate, a halogenating agent (with optional titanatingagent), a halo-malonate, and a solvent. The reaction product of a“contact step” is a procatalyst composition (or a procatalystintermediate) that is a combination of a magnesium moiety, a titaniummoiety, complexed with the halo-malonate (internal electron donor).

Halogenation (or halogenating) occurs by way of a halogenating agent. A“halogenating agent,” as used herein, is a compound that converts theprocatalyst precursor (or procatalyst intermediate) into a halide form.A “titanating agent,” as used herein, is a compound that provides thecatalytically active titanium species. Halogenation and titanationconvert the magnesium moiety present in the procatalyst precursor into amagnesium halide support upon which the titanium moiety (such as atitanium halide) is deposited.

In an embodiment, the halogenating agent is a titanium halide having theformula Ti(OR^(e))_(f)X_(h) wherein R^(e) and X are defined as above, fis an integer from 0 to 3; h is an integer from 1 to 4; and f+h is 4. Inthis way, the titanium halide is simultaneously the halogenating agentand the titanating agent. In a further embodiment, the titanium halideis TiCl₄ and halogenation occurs by way of chlorination of theprocatalyst precursor with the TiCl₄. The chlorination (and titanation)is conducted in the presence of a chlorinated or a non-chlorinatedaromatic liquid, such as dichlorobenzene, o-chlorotoluene,chlorobenzene, benzene, toluene, or xylene. In yet another embodiment,the halogenation and the titanation are conducted by use of a mixture ofhalogenating agent and chlorinated aromatic liquid comprising from 40 to60 volume percent halogenating agent, such as TiCl₄.

The reaction mixture is heated to a temperature from about 30° C. toabout 150° C. for a duration of about 2 minutes to about 100 minutesduring halogenation (chlorination).

In an embodiment, the procatalyst is made by contacting a solidchlorine-containing Mg precursor with a halogenating agent in thepresence of a halogenated malonate and optionally an electron donorcomponent.

In an embodiment, the procatalyst composition is made by two or morecontact steps.

In an embodiment, the procatalyst composition is made by way of at leastone contact step followed by at least one halogenation step.

In an embodiment, the procatalyst composition is made by way of at leastone halogenation step followed by at least one contact step.

Halo-Malonate

The halo-malonate is a 2-halo-malonate with a halogen substituent at the2-position. The 2-halo-malonate has the structure (I) below.

R₁ and R₂ are the same or different. Each of R₁ and R₂ is selected froma C₁-C₂₀ hydrocarbyl group and a substituted C₁-C₂₀ hydrocarbyl group. Xis a halogen atom selected from fluorine, chlorine, and bromine.

As used herein, the term “hydrocarbyl” or “hydrocarbon” is a substituentcontaining only hydrogen and carbon atoms, including branched orunbranched, saturated or unsaturated, cyclic, polycyclic, fused, oracyclic species, and combinations thereof. Nonlimiting examples ofhydrocarbyl groups include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-,cycloalkenyl-, cycloalkadienyl-, aryl-, alkylaryl-, and alkynyl-groups.

As used herein, the term “substituted hydrocarbyl” or “substitutedhydrocarbon” is a hydrocarbyl group that is substituted with one or morenonhydrocarbyl substituent groups. A nonlimiting example of anonhydrocarbyl substituent group is a heteroatom. As used herein, a“heteroatom” is an atom other than carbon or hydrogen. The heteroatomcan be a non-carbon atom from Groups IV, V, VI, and VII of the PeriodicTable. Nonlimiting examples of heteroatoms include: halogens (F Cl, Br,I), N, O, P, B, S, and Si. A substituted hydrocarbyl group also includesa halohydrocarbyl group and a silicon-containing hydrocarbyl group. Asused herein, the term “halohydrocarbyl” group is a hydrocarbyl groupthat is substituted with one or more halogen atoms.

The halo-malonate can be any 2-halo-malonate as set forth in Table 1. Ina further embodiment, the halo-malonate is a 2-fluoro-malonate wherein Xof structure (I) is a fluorine atom. In an embodiment, the2-fluoro-malonate is diethyl 2-fluoromalonate.

In an embodiment, the halo-malonate is 2-hydrocarbyl-2-halo-malonate.The 2-hydrocarbyl-2-halo-malonate has the structure (II) as set forthbelow.

R₁ and R₂, are the same or different. Each of R₁ and R₂ is selected froma C₁-C₂₀ hydrocarbyl group and a substituted C₁-C₂₀ hydrocarbyl group. Xis a halogen atom selected from fluorine, chlorine, and bromine.

In an embodiment, X is a fluorine atom and R₁ is a C₁-C₂₀ alkyl group.Nonlimiting examples of suitable C₁-C₂₀ alkyl group include an ethylgroup, an n-propyl group, an n-butyl group, an isobutyl group, ann-hexyl group, and a 2-ethylhexyl group. In a further embodiment, R₁ isa secondary C₃-C₂₀ alkyl group or a tertiary C₄-C₂₀ alkyl group.Nonlimiting examples of suitable secondary or tertiary C₃-C₂₀ alkylgroup include an isopropyl group, a tert-butyl group, a cyclopentylgroup, and a cyclohexyl group.

In an embodiment, X is a fluorine atom and R₁ is a C₆-C₂₀ aryl group ora C₇-C₂₀ alkylaryl group. Nonlimiting examples of suitable C₆-C₂₀ arylor C₇-C₂₀ alkylaryl group include a phenyl group, a 4-methylphenylgroup, a 4-ethylphenyl group, and a 1-naphthyl group.

In an embodiment, X is a fluorine, chlorine, or bromine atom and R₁ is asecondary C₃-C₂₀ alkyl group, a tertiary C₄-C₂₀ alkyl group, a C₆-C₂₀aryl group, or a C₇-C₂₀ alkylaryl group.

In an embodiment, R₂ is selected from a C₁-C₂₀ primary alkyl group, anda substituted or unsubstituted C₂-C₂₀ 1-alkenyl group.

The 2-hydrocarbyl-2-halo-malonate can be any 2-alkyl-2-halo-malonate asprovided in Table 1. In an embodiment, the 2-alkyl-2-halo-malonate is2-alkyl-2-fluoro-malonate such as diethyl2-cyclopentyl-2-fluoro-malonate.

In an embodiment, the 2-alkyl-2-halo-malonate isdiethyl-2-fluoro-2-cyclo-hexyl-malonate.

In an embodiment, the 2-alkyl-2-halo-malonate isdiethyl-2-fluoro-2-isopropyl-malonate.

In an embodiment, the internal electron donor is a mixed internalelectron donor. A “mixed internal electron donor” is an electron donorcomposed of (i) a halo-malonate and (ii) an electron donor component.The halo-malonate may be any halo-malonate with the structure (I)-(II)as disclosed above. An “electron donor component” is a composition otherthan the halo-malonate, added during procatalyst synthesis, whichdonates a pair of electrons to one or more metals present in theresultant procatalyst composition. The electron donor component reactswith the procatalyst precursor, the halogenating agent, (optionally thehalo-malonate) during a contact step. This forms a procatalystcomposition composed of a magnesium moiety, a titanium moiety, thehalo-malonate, and the electron donor component (i.e., a reactionproduct of the procatalyst precursor, the halogenating agent thehalo-malonate, and the electron donor component). The electron donorcomponent may contain electron-donative groups such as carboxylate,carbonate, ether, amine, amide, and carbamate. In a further embodiment,the electron donor component may be selected from aliphatic ester,aromatic ester, phthalate, 1,3-diether, succinate, malonate, cyclicaliphatic dicarboxylate, diol diester, dicarbonate, ketoester,alkoxyester, alkoxyalkyl ester, and amidoester.

In an embodiment, the electron donor component is selected from C₁-C₂₀hydrocarbyl ester or (poly)ester of C₁-C₂₀ aliphatic or aromaticcarboxylic acid. In a further embodiment, the electron donor componentis selected from ethyl acetate and bis(benzoyloxy)dimethylsilane.

Applicant has surprisingly discovered that a procatalyst compositionwith a 2-fluoro-malonate internal electron donor produces a procatalystcomposition with improved selectivity, improved catalyst activity,improved hydrogen response, and/or improved melting point when comparedto procatalyst compositions containing conventional malonate orhalo-malonate. In particular, procatalyst compositions with2-fluoro-malonate exhibit unexpected improvement in view of comparableprocatalyst compositions containing conventional malonate without 2-haloas well as chloro-malonate and/or bromo-malonate.

The present procatalyst composition, with the fluoro-malonate isphthalate-free yet exhibits similar, or improved, selectivity and/orcatalyst activity, hydrogen response, and/or melting point when comparedto phthalate-containing procatalyst compositions. These improvementsmake the present procatalyst composition suitable for commercial polymerproduction.

In an embodiment, the present procatalyst composition contains greaterthan 2 wt %, or greater than 3 wt %, or greater than 4 wt %, or greaterthan 5 wt % to 15 wt %, or 10 wt % of a 2-fluoro-malonate. Weightpercent is based on total weight of the procatalyst composition.

In an embodiment, the halo-malonate present in the procatalystcomposition is a compounded halo-malonate. A “compounded halo-malonate”as used herein, is a halo-malonate complexed to a procatalyst componentand formed by two or more contact steps during procatalyst synthesis. Ina further embodiment, the halo-malonate is a compounded fluoro-malonatethat is present in the procatalyst composition in an amount greater than2 wt %, or greater than 3 wt %, or greater than 4 wt %, or greater than5 wt % to 15 wt %, or wt %. Weight percent is based on total weight ofthe procatalyst composition.

In an embodiment, the procatalyst composition contains a compoundedmixed internal electron donor. A “compounded mixed internal electrondonor”, as used herein, is a halo-malonate and/or an electron donorcomponent complexed to a procatalyst component and formed by two or morecontact steps during procatalyst synthesis. The compounded mixedinternal electron donor is present in an amount from 2 wt % to 15 wt %.Weight percent is based on total weight of the procatalyst composition.

In an embodiment, the magnesium moiety of the procatalyst composition isa magnesium chloride. The titanium moiety of the procatalyst compositionis a titanium chloride.

The resulting procatalyst composition has a titanium content of fromabout 1.0 wt %, or about 1.5 wt %, or about 2.0 wt %, to about 6.0 wt %,or about 5.5 wt %, or about 5.0 wt %. The weight ratio of titanium tomagnesium in the solid procatalyst composition is suitably between about1:3 and about 1:160, or between about 1:4 and about 1:50, or betweenabout 1:6 and 1:30. The 2-fluoro-malonate may be present in theprocatalyst composition in a molar ratio of 2-fluoro-malonate tomagnesium of from about 0.005:1 to about 1:1, or from about 0.01:1 toabout 0.4:1. Weight percent is based on the total weight of theprocatalyst composition.

The procatalyst composition may comprise two or more embodimentsdisclosed herein.

Catalyst Composition

The present disclosure provides a catalyst composition. In anembodiment, the catalyst composition includes a procatalyst compositioncontaining a halo-malonate, a cocatalyst, and an external electrondonor. The procatalyst composition may be any of the foregoingprocatalyst compositions containing structures (I)-(II) as disclosedabove. In an embodiment, the halo-malonate is a 2-fluoro-malonate.

As used herein, a “cocatalyst” is a substance capable of converting theprocatalyst to an active polymerization catalyst. The cocatalyst mayinclude hydrides, alkyls, or aryls of aluminum, lithium, zinc, tin,cadmium, beryllium, magnesium, and combinations thereof. In anembodiment, the cocatalyst is a hydrocarbyl aluminum compoundrepresented by the formula R_(n)AlX_(3-n) wherein n=1 2, or 3, R is analkyl, and X is a halide or alkoxide. In an embodiment, the cocatalystis selected from trimethylaluminum, triethylaluminum,triisobutylaluminum, and tri-n-hexylaluminum.

Nonlimiting examples of suitable hydrocarbyl aluminum compounds are asfollows: methylaluminoxane, isobutylaluminoxane, diethylaluminumethoxide, diisobutylaluminum chloride, tetraethyldialuminoxane,tetraisobutyldialuminoxane, diethylaluminum chloride, ethylaluminumdichloride, methylaluminum dichloride, dimethylaluminum chloride,triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride,di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminumdihydride, diisobutylhexylaluminum, isobutyldihexylaluminum,trimethylaluminum, triethylaluminum, tri-n-propylaluminum,triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum,tri-n-decylaluminum, tri-n-dodecylaluminum, diisobutylaluminum hydride,and di-n-hexylaluminum hydride.

In an embodiment, the cocatalyst is triethylaluminum. The molar ratio ofaluminum to titanium is from about 5:1 to about 500:1, or from about10:1 to about 200:1, or from about 15:1 to about 150:1, or from about20:1 to about 100:1. In another embodiment, the molar ratio of aluminumto titanium is about 45:1.

As used herein, an “external electron donor” (or “EED”) is a compoundadded independent of procatalyst formation and includes at least onefunctional group that is capable of donating a pair of electrons to ametal atom. Bounded by no particular theory, it is believed thatprovision of one or more external electron donors in the catalystcomposition affects the following properties of the formant polymer:level of tacticity (i.e., xylene soluble material), molecular weight(i.e., melt flow), molecular weight distribution (MWD), melting point,and/or oligomer level.

In an embodiment, the EED is a silicon compound having the generalformula (III):SiR_(m)(OR′)_(4-m)  (III)

wherein R independently each occurrence is hydrogen or a hydrocarbyl oran amino group, optionally substituted with one or more substituentscontaining one or more Group 14, 15, 16, or 17 heteroatoms. R containsup to 20 atoms not counting hydrogen and halogen. R′ is a C₁₋₂₀ alkylgroup, and m is 0, 1, 2, or 3. In an embodiment, R is C₆₋₁₂ aryl,aralkyl or alkylaryl, C₃₋₁₂ cycloalkyl, C₃₋₁₂ branched alkyl, or C₂₋₁₂cyclic amino group, R′ is C₁₋₄ alkyl, and m is 1 or 2.

In an embodiment, the silicon compound is dicyclopentyldimethoxysilane(DCPDMS), methylcyclohexyldimethoxysilane (MChDMS), orn-propyltrimethoxysilane (NPTMS), and any combination thereof.

In an embodiment, the present catalyst composition includes an activitylimiting agent (ALA). An “activity limiting agent,” as used herein is amaterial that reduces catalyst activity at elevated temperature, namely,in a polymerization reactor at polymerization conditions at atemperature greater than about 100° C. Provision of the ALA results in aself-limiting catalyst composition. As used herein, a “self-limiting”catalyst composition is a catalyst composition that demonstratesdecreased activity at a temperature greater than about 100° C. In otherwords, “self-limiting” is the significant decline of catalyst activitywhen the reaction temperature rises above 100° C. compared to thecatalyst activity under normal polymerization conditions with reactiontemperature usually below 80° C. In addition, as a practical standard,if a polymerization process, such as a fluidized bed, gas-phasepolymerization running at normal processing conditions is capable ofinterruption and resulting collapse of the bed with reduced risk withrespect to agglomeration of polymer particles, the catalyst compositionis said to be “self-limiting.”

The ALA may be an aromatic ester or a derivative thereof, an aliphaticester or derivative thereof, a diether, a poly(alkylene glycol) ester,and combinations thereof. Nonlimiting examples of suitable aromaticesters include C₁₋₁₀ alkyl or cycloalkyl esters of aromaticmonocarboxylic acids. Suitable substituted derivatives thereof includecompounds substituted both on the aromatic ring(s) or the ester groupwith one or more substituents containing one or more Group 14, 15 or 16heteroatoms, especially oxygen. Examples of such substituents include(poly)alkylether, cycloalkylether, arylether, aralkylether,alkylthioether, arylthioether, dialkylamine, diarylamine,diaralkylamine, and trialkylsilane groups. The aromatic carboxylic acidester may be a C₁₋₂₀ hydrocarbyl ester of benzoic acid wherein thehydrocarbyl group is unsubstituted or substituted with one or more Group14, 15 or 16 heteroatom containing substituents and C₁₋₂₀(poly)hydrocarbyl ether derivatives thereof, or C₁₋₄ alkyl benzoates andC₁₋₄ ring alkylated derivatives thereof, or methyl benzoate, ethylbenzoate, propyl benzoate, methyl p-methoxybenzoate, methylp-ethoxybenzoate, ethyl p-methoxybenzoate, and ethyl p-ethoxybenzoate.In an embodiment, the aromatic carboxylic acid ester is ethylp-ethoxybenzoate.

In an embodiment, the ALA is an aliphatic ester. The aliphatic ester maybe a C₄₋₃₀ aliphatic acid ester, may be a mono- or a poly- (two or more)ester, may be straight chain or branched, may be saturated orunsaturated, and any combination thereof. The C₄₋₃₀ aliphatic acid estermay also be substituted with one or more Group 14, 15 or 16 heteroatomcontaining substituents. Nonlimiting examples of suitable C₄₋₃₀aliphatic acid esters include C₁₋₂₀ alkyl esters of aliphatic C₄₋₃₀monocarboxylic acids, C₁₋₂₀ alkyl esters of aliphatic C₈₋₂₀monocarboxylic acids, C₁₋₄ alkyl mono- and diesters of aliphatic C₄₋₂₀monocarboxylic acids and dicarboxylic acids, C₁₋₄ alkyl esters ofaliphatic C₈₋₂₀ monocarboxylic acids and dicarboxylic acids, and C₄₋₂₀mono- or polycarboxylate derivatives of C₂₋₁₀₀ (poly)glycols or C₂₋₁₀₀(poly)glycol ethers. In a further embodiment, the C₄₋₃₀ aliphatic acidester may be isopropyl myristate and/or di-n-butyl sebacate.

In an embodiment, the ALA is isopropyl myristate.

In an embodiment, the ALA is a diether. The diether may be a dialkyldiether represented by the following formula:

wherein R₁ to R₄ are independently of one another an alkyl, aryl oraralkyl group having up to 20 carbon atoms, which may optionally containa group 14, 15, 16, or 17 heteroatom, provided that R₁ and R₂ may be ahydrogen atom.

In an embodiment, the ALA is a poly(alkylene glycol) ester. Nonlimitingexamples of suitable poly(alkylene glycol) esters include poly(alkyleneglycol) mono- or diacetates, poly(alkylene glycol) mono- ordi-myristates, poly(alkylene glycol) mono- or di-laurates, poly(alkyleneglycol) mono- or di-oleates, glyceryl tri(acetate), glyceryl tri-esterof C₂₋₄₀ aliphatic carboxylic acids, and any combination thereof. In anembodiment, the poly(alkylene glycol) moiety of the poly(alkyleneglycol) ester is a poly(ethylene glycol).

The present catalyst composition may comprise two or more embodimentsdisclosed herein.

In an embodiment, a polymerization process is provided. Thepolymerization process includes contacting propylene and optionally atleast one other olefin with a catalyst composition in a polymerizationreactor under polymerization conditions. The catalyst composition may beany catalyst composition disclosed herein and includes a procatalystcomposition with a halo-malonate internal electron donor, a cocatalyst,and an external electron donor. The process also includes forming apropylene-based polymer. The propylene-based polymer contains thehalo-malonate.

In an embodiment, the halo-malonate is a 2-fluoro-malonate having astructure (I)-(II) above. The process includes forming a propylene-basedpolymer that contains fluorine and has a T_(MF) greater than 170° C., orfrom greater than 170° C. to 173° C.

In an embodiment, the process includes forming a propylene-based polymercontaining a 2-fluoro-malonate and having a melt flow rate greater than1 g/10 min, or greater than 10 g/10 min, or greater than 25 g/10 min, orgreater than 50 g/10 min, or greater than 75 g/10 min, or greater than100 g/10 min to 2000 g/10 min, or 1000 g/10 min, or 500 g/10 min, or 400g/10 min, or 200 g/10 min.

The process includes contacting propylene and optionally at least oneother olefin with the catalyst composition in a polymerization reactor.One or more olefin monomers can be introduced into the polymerizationreactor along with the propylene to react with the catalyst and to forma polymer, a copolymer, (or a fluidized bed of polymer particles).Nonlimiting examples of suitable olefin monomers include ethylene, C₄₋₂₀α-olefins, such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,1-heptene, 1-octene, 1-decene, 1-dodecene and the like; C₄₋₂₀ diolefins,such as 1,3-butadiene, 1,3-pentadiene, norbornadiene,5-ethylidene-2-norbornene (ENB) and dicyclopentadiene; C₈₋₄₀ vinylaromatic compounds including styrene, o-, m-, and p-methylstyrene,divinylbenzene, vinylbiphenyl, vinylnapthalene; and halogen-substitutedC₈₋₄₀ vinyl aromatic compounds such as chlorostyrene and fluorostyrene.

In an embodiment, the process includes contacting propylene with thecatalyst composition to form a propylene homopolymer.

As used herein, “polymerization conditions” are temperature and pressureparameters within a polymerization reactor suitable for promotingpolymerization between the catalyst composition and an olefin to formthe desired polymer. The polymerization process may be a gas phase, aslurry, or a bulk polymerization process, operating in one, or more thanone, polymerization reactor. Accordingly, the polymerization reactor maybe a gas phase polymerization reactor, a liquid-phase polymerizationreactor, or a combination thereof.

It is understood that provision of hydrogen in the polymerizationreactor is a component of the polymerization conditions. Duringpolymerization, hydrogen is a chain transfer agent and affects themolecular weight (and correspondingly the melt flow rate) of theresultant polymer.

In an embodiment, polymerization occurs by way of liquid phasepolymerization.

In an embodiment, polymerization occurs by way of gas phasepolymerization. As used herein, “gas phase polymerization” is thepassage of an ascending fluidizing medium, the fluidizing mediumcontaining one or more monomers, in the presence of a catalyst through afluidized bed of polymer particles maintained in a fluidized state bythe fluidizing medium. “Fluidization,” “fluidized,” or “fluidizing” is agas-solid contacting process in which a bed of finely divided polymerparticles is lifted and agitated by a rising stream of gas. Fluidizationoccurs in a bed of particulates when an upward flow of fluid through theinterstices of the bed of particles attains a pressure differential andfrictional resistance increment exceeding particulate weight. Thus, a“fluidized bed” is a plurality of polymer particles suspended in afluidized state by a stream of a fluidizing medium. A “fluidizingmedium” is one or more olefin gases, optionally a carrier gas (such asH₂ or N₂) and optionally a liquid (such as a hydrocarbon) which ascendsthrough the gas-phase reactor.

A typical gas-phase polymerization reactor (or gas phase reactor)includes a vessel (i.e., the reactor), the fluidized bed, a distributionplate, inlet and outlet piping, a compressor, a cycle gas cooler or heatexchanger, and a product discharge system. The vessel includes areaction zone and a velocity reduction zone, each of which is locatedabove the distribution plate. The bed is located in the reaction zone.In an embodiment, the fluidizing medium includes propylene gas and atleast one other gas such as an olefin and/or a carrier gas such ashydrogen or nitrogen.

In an embodiment, the contacting occurs by way of feeding the catalystcomposition into the polymerization reactor and introducing the olefininto the polymerization reactor. In an embodiment, the process includescontacting the olefin with a cocatalyst. The cocatalyst can be mixedwith the procatalyst composition (pre-mix) prior to the introduction ofthe procatalyst composition into the polymerization reactor. In anotherembodiment, cocatalyst is added to the polymerization reactorindependently of the procatalyst composition. The independentintroduction of the cocatalyst into the polymerization reactor can occursimultaneously, or substantially simultaneously, with the procatalystcomposition feed.

The present disclosure provides a polymeric composition. The polymericcomposition may be made by any of the foregoing polymerizationprocesses. In an embodiment, a polymeric composition is provided andincludes a propylene-based polymer containing a 2-fluoro-malonate. Thepropylene-based polymer has a T_(MF) greater than 170° C., or greaterthan 172° C., or from greater than 170° C. to 173° C.

In an embodiment, the propylene-based polymer has a melt flow rategreater than 1 g/10 min. In a further embodiment, the propylene-basedpolymer has a melt flow rate greater than 10 g/10 min, or greater than25 g/10 min, or greater than 50 g/10 min, or greater than 75 g/10 min,or greater than 100 g/10 min to 2000 g/10 min, or 1000 g/10 min, or 500g/10 min, or 400 g/10 min, or 200 g/10 min.

In an embodiment, the polymeric composition has a melt flow rate greaterthan 25 g/10 min.

In an embodiment, the propylene-based polymer has a xylene solublescontent from 1 wt % to 4 wt % weight percent is based on total weight ofthe propylene-based polymer.

In an embodiment, the polymeric composition is a propylene homopolymer.

In an embodiment, the polymeric composition is a propylene copolymer(such as a propylene/ethylene copolymer).

The present polymerization process and/or the present polymercomposition may comprise two or more embodiments disclosed herein.

DEFINITIONS

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Groups or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference),especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

Any numerical range recited herein, includes all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent, or a value of a compositional or a physical property, suchas, for example, amount of a blend component, softening temperature,melt index, etc., is between 1 and 100, it is intended that allindividual values, such as, 1, 2, 3, etc., and all subranges, such as, 1to 20, 55 to 70, 197 to 100, etc., are expressly enumerated in thisspecification. For values which are less than one, one unit isconsidered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These areonly examples of what is specifically intended, and all possiblecombinations of numerical values between the lowest value and thehighest value enumerated, are to be considered to be expressly stated inthis application. In other words, any numerical range recited hereinincludes any value or subrange within the stated range. Numerical rangeshave been recited, as discussed herein, reference melt index, melt flowrate, and other properties.

The term “alkyl,” as used herein, refers to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Nonlimitingexamples of suitable alkyl radicals include, for example, methyl, ethyl,n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), etc.The alkyls have 1 and 20 carbon atoms.

The term “aryl,” as used herein, refers to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. The aryls have 1 and20 carbon atoms.

The terms “blend” or “polymer blend,” as used herein, is a blend of twoor more polymers. Such a blend may or may not be miscible (not phaseseparated at molecular level). Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and other methods known in the art.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “comprising,” and derivatives thereof, is not intended toexclude the presence of any additional component, step or procedure,whether or not the same is disclosed herein. In order to avoid anydoubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compoundwhether polymeric or otherwise, unless stated to the contrary. Incontrast, the term, “consisting essentially of” excludes from the scopeof any succeeding recitation any other component, step or procedure,excepting those that are not essential to operability. The term“consisting of” excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized ethylene monomer(based on the total weight of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term “interpolymer,” as used herein, refers to polymers prepared bythe polymerization of at least two different types of monomers. Thegeneric term interpolymer thus includes copolymers, usually employed torefer to polymers prepared from two different monomers, and polymersprepared from more than two different types of monomers.

The term “olefin-based polymer” is a polymer containing, in polymerizedform, a majority weight percent of an olefin, for example ethylene orpropylene, based on the total weight of the polymer. Nonlimitingexamples of olefin-based polymers include ethylene-based polymers andpropylene-based polymers.

The term “polymer” is a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike.

A “primary alkyl group” has the structure —CH₂R₁ wherein R₁ is hydrogenor a substituted/unsubstituted hydrocarbyl group.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized propylene monomer(based on the total amount of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

A “secondary alkyl group” has the structure —CHR₁R₂ wherein each of R₁and R₂ is a substituted/unsubstituted hydrocarbyl group.

The term “substituted alkyl,” as used herein, refers to an alkyl as justdescribed in which one or more hydrogen atom bound to any carbon of thealkyl is replaced by another group such as a halogen, aryl, substitutedaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halogen, haloalkyl, hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

A “tertiary alkyl group” has the structure —CR₁R₂R₃ wherein each of R₁,R₂, and R₃ is a substituted/unsubstituted hydrocarbyl group.

Test Methods

Final melting point T_(MF) is the temperature to melt the most perfectcrystal in the sample and is regarded as a measure for isotacticity andinherent polymer crystallizability. The test was conducted using a TAQ100 Differential Scanning calorimeter. A sample is heated from 0° C. to240° C. at a rate of 80° C./min, cooled at the same rate to 0° C., thenheated again at the same rate up to 150° C., held at 150° C. for 5minutes and the heated from 150° C. to 180° C. at 1.25° C./min. TheT_(MF) is determined from this last cycle by calculating the onset ofthe baseline at the end of the heating curve.

Testing Procedure:

-   -   (1) Calibrate instrument with high purity indium as standard.    -   (2) Purge the instrument head/cell with a constant 50 ml/min        flow rate of nitrogen constantly.    -   (3) Sample preparation:        -   Compression mold 1.5 g of powder sample using a            30-G302H-18-CX Wabash Compression Molder (30 ton): (a) heat            mixture at 230° C. for 2 minutes at contact; (b) compress            the sample at the same temperature with 20 ton pressure for            1 minute; (c) cool the sample to 45° F. and hold for 2            minutes with 20 ton pressure; (d) cut the plaque into 4 of            about the same size, stack them together, and repeat steps            (a)-(c) in order to homogenize sample.    -   (4) Weigh a piece of sample (preferably between 5 to 8 mg) from        the sample plaque and seal it in a standard aluminum sample pan.        Place the sealed pan containing the sample on the sample side of        the instrument head/cell and place an empty sealed pan in the        reference side. If using the auto sampler, weigh out several        different sample specimens and set up the machine for a        sequence.    -   (5) Measurements:        -   (i) Data storage: off        -   (ii) Ramp 80.00° C./min to 240.00° C.        -   (iii) Isothermal for 1.00 min        -   (iv) Ramp 80.00° C./min to 0.00° C.        -   (v) Isothermal for 1.00 min        -   (vi) Ramp 80.00° C./min to 150.00° C.        -   (vii) Isothermal for 5.00 min        -   (viii) Data storage: on        -   (ix) Ramp 1.25° C./min to 180.00° C.        -   (x) End of method    -   (6) Calculation: T_(MF) is determined by the interception of two        lines. Draw one line from the base-line of high temperature.        Draw another line from through the deflection of the curve close        to the end of the curve at high temperature side.

Melt flow rate (MFR) is measured in accordance with ASTM D 1238-01 testmethod at 230° C. with a 2.16 kg weight for propylene-based polymers.

Polydispersity Index (PDI) is measured by an AR-G2 rheometer which is astress control dynamic spectrometer manufactured by TA Instruments usinga method according to Zeichner GR, Patel PD (1981) “A comprehensiveStudy of Polypropylene Melt Rheology” Proc. Of the 2nd World Congress ofChemical Eng., Montreal, Canada. An ETC oven is used to control thetemperature at 180° C.±0.1° C. Nitrogen is used to purge the inside theoven to keep the sample from degradation by oxygen and moisture. A pairof 25 mm in diameter cone and plate sample holder is used. Samples arecompress molded into 50 mm×100 mm×2 mm plaque. Samples are then cut into19 mm square and loaded on the center of the bottom plate. Thegeometries of upper cone is (1) Cone angle: 5:42:20 (deg:min:I); (2)Diameter: 25 mm; (3) Truncation gap: 149 micron. The geometry of thebottom plate is 25 mm cylinder.

Testing Procedure:

-   -   (1) The cone & plate sample holder are heated in the ETC oven at        180° C. for 2 hours. Then the gap is zeroed under blanket of        nitrogen gas.    -   (2) Cone is raised to 2.5 mm and sample loaded unto the top of        the bottom plate.    -   (3) Start timing for 2 minutes.    -   (4) The upper cone is immediately lowered to slightly rest on        top of the sample by observing the normal force.    -   (5) After two minutes the sample is squeezed down to 165 micron        gap by lower the upper cone.    -   (6) The normal force is observed. When the normal force is down        to <0.05 Newton the excess sample is removed from the edge of        the cone and plate sample holder by a spatula.    -   (7) The upper cone is lowered again to the truncation gap which        is 149 micron.    -   (8) An Oscillatory Frequency Sweep test is performed under these        conditions:        -   Test delayed at 180° C. for 5 minutes.        -   Frequencies: 628.3 r/s to 0.1 r/s.        -   Data acquisition rate: 5 point/decade.        -   Strain: 10%    -   (9) When the test is completed the crossover modulus (Gc) is        detected by the Rheology Advantage Data Analysis program        furnished by TA Instruments.    -   (10) PDI=100,000÷Gc (in Pa units).

Xylene Solubles (XS) is measured using a ¹H NMR method as described inU.S. Pat. No. 5,539,309, the entire content of which is incorporatedherein by reference.

By way of example and not by limitation, examples of the presentdisclosure will now be provided.

EXAMPLES 1. Procatalyst Precursor

MagTi-1 is used as a procatalyst precursor. MagTi-1 is a mixed Mg/Tiprecursor with composition of Mg₃Ti(OEt)₈Cl₂ (prepared according toexample 1 in U.S. Pat. No. 6,825,146). Titanium content for each of theresultant procatalyst compositions is listed in Table 1. The peaks forinternal donors are assigned according to retention time from GCanalysis.

A. First Contact

3.00 g of MagTi-1 is charged into a flask equipped with mechanicalstirring and with bottom filtration. 60 ml of a mixed solvent of TiCl₄and chlorobenzene (1/1 by volume) is introduced into the flask followedimmediately by addition of 2.52 mmol of malonate (includinghalo-malonate and/or malonate) or DiBP. The mixture is heated to 115° C.in 15 minutes and remains at 115° C. for 60 minutes with stirring at 250rpm before filtering off the liquid.

B. Second Contact/Halogenation

60 ml of mixed solvent and optionally 2.52 mmol of (halo-)malonate areadded again and the reaction is allowed to continue at the same desiredtemperature for 30 minutes with stirring followed by filtration.

C. Third Contact/Halogenation

Same as step (B) above.

The final procatalyst composition is rinsed three times at roomtemperature with 70 ml of isooctane and dried under nitrogen flow for 2hours.

Procatalyst properties are set forth in Table 1 below. Weight percent isbased on total weight of the procatalyst composition. The data in Table1 are based on MagTi-1 as the procatalyst precursor. Abbreviations inTable 1 indicate the following: MA—malonate or halo-malonate,EtO—Ethoxide, ID—Internal Electron Donor (complexed form of MA or DiBPin procatalyst), EB—Ethyl Benzoate, DiBP—Diisobutyl Phthalate. Wt % isbased on total weight of the procatalyst composition.

DiBP in Table 1 is a comparative sample.

TABLE 1 Ti EtO ID Ref # Structure 1^(st) MA Addition 2^(nd) MA Addition(%) (%) (%) 1

2.52 2.21 0.37 2.72 2

2.52 1.50 0.60 1.69 3

2.52 2.76 0.71 1.76 4

2.52 2.52 0.33 8.81 5

2.52 2.92 0.40 2.46 6

2.52 2.09 0.34 4.61 7

2.52 2.45 0.29 9.06 8

2.52 2.96 0.29 10.74 9

2.52 2.52 2.52 2.93 2.57 0.44 0.38 8.71 10.48 10

2.52 2.52 2.52 3.26 2.50 0.25 0.28 10.12 11.45 11

2.52 2.52 2.52 2.65 2.68 0.43 0.33 11.85 10.48 DiBP

2.52 3.04 0.18 12.36 12

2.52 2.52 2.52 2.82 2.46 0.53 0.35 10.83 9.07 13

2.52 2.52 2.52 3.27 2.09 0.31 0.49 9.33 10.66 14

2.52 2.25 2.52 3.08 2.22 0.36 0.29 9.38 9.42 15

2.52 2.52 2.52 2.93 1.92 0.54 0.46 9.12 7.93

2. Polymerization

Polymerization is performed in liquid propylene in a 1-gallon autoclave.After conditioning, the reactor is charged with 1375 g of propylene anda targeted amount of hydrogen and brought to 62° C. 0.25 mmol ofdicyclopentyldimethoxysilane (or n-propyltrimethyoxysilane) is added to7.2 ml of a 0.27 M triethylaluminum solution in isooctane, followed byaddition of a 5.0 wt % procatalyst slurry in mineral oil (actual solidweight is indicated in Table 2 below). The mixture is premixed atambient temperature for 20 minutes before being injected into thereactor to initiate the polymerization. The premixed catalyst componentsare flushed into the reactor with isooctane using a high pressurecatalyst injection pump. After the exotherm, the temperature ismaintained at 67° C. Total polymerization time was 1 hour.

Polymer samples are tested for melt flow rate (MFR), xylene solubles(XS), polydispersity index (PDI), and final melting point (T_(MF)). XSis measured using ¹H NMR method.

DiBP in any of Tables 2-8 is a comparative sample.

Catalyst performance and polymer properties are provided in Table 2-8below. Weight percent is based on total weight of the polymer.Abbreviations in Tables 2-8 indicate the following.

-   -   NM=Not measured    -   N/A=Not available    -   D=Dicyclopentyldimethoxysilane    -   N=N-propyltrimethyoxysilane

TABLE 2 Catalyst Performance and Polymer Properties of HalogenatedMalonates Activity MFR Ref Number of (kg/g- (g/10 XS T_(MF) # StructureID Additions hr) min) (%) PDI (° C.) 1 

1 13.0 3.7 7.42 5.25 171.03 2*

1 15.9 4.5 8.01 5.36 170.56 3*

1 14.7 5.0 8.36 5.24 170.68 *Comparative DCPDMS is used as EED. 16.7 mgof procatalyst and 67 mmol of H₂ are used for each polymerization test.

Results in Table 2 show that among the simple halogenated malonates thefluorine derivative (1) has the best selectivity with good catalystactivity.

TABLE 3 Catalyst Performance and Polymer Properties of HalogenatedMethylmalonates Number of Activity MFR Ref ID (kg/g- (g/10 XS T_(MF) #Structure Additions hr) min) (%) PDI (° C.) 4 

1 18.6 2.8 5.68 4.89 171.62 5*

1 18.7 4.1 8.37 5.23 170.92 6*

1 19.9 2.7 6.15 5.17 171.26 7*

1 21.1 3.6 6.86 5.16 171.11 *Comparative DCPDMS is used as EED. 16.7 mgof procatalyst and 67 mmol of H₂ are used for each polymerization test.

For methylmalonates, substitution with a chlorine atom (5) leads tohigher XS and bromine (6) leads to lower XS. However, the lowest XS isobtained with fluorine substitution (4).

TABLE 4 Catalyst Performance and Polymer Properties of HalogenatedCyclopentylmalonates Number of Activity MFR Ref ID (kg/g- (g/10 XST_(MF) # Structure Additions hr) min) (%) PDI (° C.) 8 

1 25.3 1.9 3.28 4.54 172.05 9 

1 2 27.8 25.5 2.4 1.8 4.83 3.17 4.52 4.44 172.09 172.39 10*

1 2 28.6 29.9 2.8 2.0 5.67 5.15 4.77 4.84 170.77 171.46 11*

1 2 25.2 15.3 3.3 2.1 4.94 3.56 4.99 4.98 171.11 171.34 DiBP*

1 32.9 1.8 3.87 4.68 171.92 *Comparative DCPDMS is used as EED. 16.7 mgof procatalyst and 67 mmol of H₂ are used for each polymerization test.

Chlorine substitution of cyclopentylmalonate (9) leads to improvement inXS over the unsubstituted compound (II) as well as themethyl-substituted compound (10).

Procatalyst made by double addition of the chlorinated malonate (9)produces polymer with improvement properties compared to the DiBPprocatalyst (XS and T_(MF)).

The fluorinated derivative (8) exhibits the best performance forprocatalysts made from a single contact step during procatalystsynthesis.

TABLE 5 Comparison of Catalyst Performance between Diethyl2-Cyclopentyl-2- fluoromalonate (8) and DiBP Activity MFR H₂ (kg/g-(g/10 XS T_(MF) Ref # Structure EED (mmol) hr) min) (%) PDI (° C.) 8

D D D D  67 446 670 893 22.0 17.0 33.1 30.4  2.6 27.4 61.6 77.6 2.701.98 2.33 2.12 4.52 4.82 4.76 4.77 172.20 171.30 171.00 170.64 DiBP*

D D D D  67 446 670 893 30.1 21.3 16.8 22.9  2.3 26.8 43.2 74.2 3.822.31 1.78 1.77 4.67 5.29 5.41 5.26 172.27 171.24 171.19 170.81 8

N N N  45 313 436  8.8 11.2 14.8  3.2 40.8 98.2 2.23 2.30 2.31 4.02 4.384.42 170.48 170.36 169.30 DiBP*

N N N  45 313 436 12.4 14.3 12.1  3.7 23.4 89.4 2.37 2.28 2.38 4.14 4.634.57 170.40 169.76 169.41 *Comparative 8.4 mg of procatalyst is used foreach polymerization test.

The performance of compound 8 is overall quite close to DiBP in regardof catalyst activity, XS, H₂ response, and T_(MF), except that PDIremains almost the same regardless of MF changing while PDI for DiBPcatalyst increases with MF. The narrower PDI is beneficial for someend-use applications, such as fiber, biaxially oriented polypropylene,and thin-walled injection molding.

TABLE 6 Catalyst Performance and Polymer Properties of Other HalogenatedMalonates Number of Activity MFR Ref ID (kg/g- (g/10 XS T_(MF) #Structure Additions hr) min (%) PDI (° C.) 12

1 2 22.4 23.9 3.5 2.4 5.38 4.33 4.99 170.67 13

1 2 17.7 22.6 2.7 NM 3.13 3.44 4.66 4.89 171.05 171.88 14

1 2 26.4 24.4 3.6 2.4 5.88 4.57 5.00 4.84 170.87 171.68 15

1 2 22.6 20.1 3.1 2.3 4.9  4.2  4.82 4.80 170.51 171.44 DCPDMS is usedas EED. 16.7 mg of procatalyst and 67 mmol of H₂ are used for eachpolymerization test.

These fluorinated hydrocarbyl-substituted malonates (Ref. #'s 12-15)show good activity and good isotacticity selectivity. Furthermore,improved XS is obtained via multiple donor additions. Compound 13 showsbest performance among the group, and similar to compound 8.

TABLE 7 Effects of Ethyl Acetate as a Secondary Donor Number ActivityMFR of H₂ (kg/g- (g/10 XS T_(MF) Ref # Structure Additives SCA (mmol)hr) min) (%) PDI (° C.) DiBP*

1 D D 446 670 36.5 31.8  25.8  36.8 2.60 2.16 4.83 4.85 170.88 170.818 + EtOAc

1 D D 446 670 31.9 27.0  27.9  53.9 2.57 2.16 4.76 170.77 170.53 2 D D446 670 22.1 28.0 NM  54.9 1.90 1.70 4.71 4.60 170.74 170.52 DiBP*

1 N N 446 670 15.5 11.5  61.5 110.1 2.54 2.45 4.79 4.82 169.54 169.398 + EtOAc

1 N N 446 670 25.3  9.0  80.9 145.1 2.49 2.56 4.18 5.04 169.40 169.27 2N N 446 670 14.8  8.8  90.4 158.4 2.46 2.09 4.12 4.87 169.82 169.27*Comparative 11 mg of procatalyst is used for each polymerization test.EtOAc = Ethyl Acetate NM = Not measured

When ethyl acetate (EtOAc) is used as a secondary donor, the resultingcatalyst shows good activity and good selectivity, comparable to theDiBP catalyst. Surprisingly, H₂ response is significantly improved,especially at high H₂ level. The procatalyst made by double donoraddition (i.e., catalyst composition containing compoundedhalo-malonate) displays obvious improvement in XS, especially when Ddonor is used.

TABLE 8 Effects of Halogenated Malonate as a Secondary Donor IDCompositions (mol %) Activity MFR Compound Procatalyst H₂ (kg/g- (g/10XS T_(MF) 8 BBzSi EED (mg) (mmol) hr) min) (%) PDI (° C.) 0 100 D 16.7446 8.9 11.7 2.48 6.22 171.26 25 75 D 16.7 446 19.8 9.4 2.66 5.44 171.2450 50 D 16.7 446 27.5 5.9 2.71 5.60 171.71 75 25 D 16.7 446 35.2 8.02.86 5.22 172.00 100 0 D 8.4 446 17.0 27.4 1.98 4.82 171.30 0 100 N 16.7268 5.9 4.1 1.09 6.48 170.88 25 75 N 16.7 268 18.4 4.0 1.02 5.97 170.8450 50 N 16.7 268 23.4 5.8 1.68 5.60 171.01 75 25 N 16.7 268 17.1 5.21.17 5.40 169.83 100 100 N 8.4 313 11.2 40.8 2.3 4.38 170.36 BBzSi =Bis(benzyloxy)dimethylsilane *Comparative

BenMag precursor is typically used as procatalyst precursor when BBzSiis used as internal electron donor because BBzSi typically exhibits pooractivity with other precursors. Through a combination of a MagTiprecursor, a halogenated malonate (8) and BBzSi as internal electrondonor, it is possible to achieve a balance for catalyst activity, XS,T_(MF), and PDI so that the catalyst becomes commercially viable.

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

What is claimed is:
 1. A polymeric composition comprising: apropylene-based polymer comprising a halo-malonate with the structure(II)

wherein R₁ is selected from the group consisting of a C₃-C₂₀ secondaryalkyl group, a C₄-C₂₀ tertiary alkyl group, a C₆-C₂₀ aryl group, and aC₇-C₂₀ alkylaryl group; R₂ is selected from the group consisting of aC₁-C₂₀ primary alkyl group, and a substituted or unsubstituted C₂-C₂₀1-alkenyl group; X is selected from the group consisting of fluorine,chlorine, bromine, and iodine; and the propylene-based polymer has amelt flow rate greater than 50 g/10 min.
 2. The polymeric composition ofclaim 1 wherein the propylene-based polymer has a xylene solublescontent from 1 wt % to 4 wt %.
 3. The polymeric composition of claim 1wherein the propylene-based polymer comprises fluorine.
 4. The polymericcomposition of claim 1 wherein the propylene-based polymer is selectedfrom the group consisting of a propylene homopolymer and a propylenecopolymer.
 5. The polymeric composition of claim 1 wherein thepropylene-based polymer is a propylene homopolymer.
 6. The polymericcomposition of claim 1 wherein R₁ is selected from the group consistingof an isopropyl group, a cyclopentyl group, and a cyclohexyl group, andR₂ is an ethyl group.
 7. The polymeric composition of claim 1 comprisingan electron donor component.
 8. The polymeric composition of claim 1wherein the propylene-based polymer comprises a member selected from thegroup consisting of an alkoxysilane, an aliphatic acid ester, andcombinations thereof.
 9. A polymeric composition comprising: apropylene-based polymer having a fluoromalonate with the structure (II)

wherein R₁ and R₂ are the same or different, and further wherein R₁ isselected from the group consisting of a C₃-C₂₀ secondary alkyl group, aC₄-C₂₀ tertiary alkyl group, a C₆-C₂₀ aryl group, and a C₇-C₂₀ alkylarylgroup; and R₂ is selected from the group consisting of a C₁-C₂₀ primaryalkyl group and a substituted or unsubstituted C₂-C₂₀ 1-alkenyl group.10. The polymeric composition of claim 9 wherein R₁ is selected from thegroup consisting of an isopropyl group, a tert-butyl, a cyclohexylgroup, and a cyclopentyl group.
 11. The polymeric composition of claim 9wherein the 2-fluoro-malonate comprises diethyl2-fluoro-2-cyclohexyl-malonate.
 12. The polymeric composition of claim 9wherein the 2-fluoro-malonate comprises diethyl2-fluoro-2-isopropyl-malonate.
 13. The polymeric composition of claim 9wherein the 2-fluoro-malonate comprises diethyl2-cyclopentyl-2-fluoro-malonate.
 14. The polymeric composition of claim9 comprising an electron donor component.
 15. The polymeric compositionof claim 14 wherein the electron donor component is selected from thegroup consisting of ethyl acetate and bis(benzoyloxy)dimethylsilane. 16.The polymeric composition of claim 9 wherein the propylene-based polymerhas a final melting point (T_(MF)) greater than 170° C.
 17. Thepolymeric composition of claim 9 wherein the propylene-based polymer hasmelt flow rate greater than 50 g/10 min.
 18. The polymeric compositionof claim 9 wherein the propylene-based polymer is selected from thegroup consisting of a propylene homopolymer and a propylene copolymer.19. The polymeric composition of claim 9 wherein the propylene-basedpolymer is a propylene homopolymer.
 20. The polymeric composition ofclaim 9 wherein the propylene-based polymer comprises a member selectedfrom the group consisting of an alkoxysilane, an aliphatic acid ester,and combinations thereof.